Process for producing thermoplastic resins

ABSTRACT

A process for producing a graft co- or terpolymeric thermoplastic resin consisting of an ethylene-propylene rubber and an aromatic vinyl compound or of an ethylene-propylene rubber, an aromatic vinyl compound and a vinyl cyanide compound, characterized by subjecting these materials to solution polymerization in a mixed solvent comprising an aromatic hydrocarbon solvent capable of dissolving the ethylene-propylene rubber and a polar solvent capable of dissolving poly-(aromatic vinyl compound) in the case of the graft-copolymer or aromatic vinyl compound-vinyl cyanide compound copolymer in the case of the graft-terpolymer. The graft-copolymer or graft-terpolymer obtained by the present process is excellent in weather resistance and impact resistance. The impact resistance of the present graft co- or ter-polymer is not affected by processing conditions.

United States Patent 1 1 Morimoto et a1.

[ Sept. 9, 1975 1 PROCESS FOR PRODUCING THERMOPLASTIC RESINS [73] Assignee: Sumitomo Chemical Company,

Limited, Osaka, Japan [22] Filed: Jan. 15, 1973 [21] Appl. No.: 323,715

3,538,192 11/1970 Bishop 3,538.193 11/1970 Meredith... 260/878 R 3,642,950 2/1972 OShea 260/878 R 3,657,395 4/1972 Meredith ct a1. 260/878 R Meredith et a1. 260/878 R Meredith et a1. 260/878 R Primary Examiner-Joseph L. Schofer Assistant ExdminerA. Holler Attorney, Agent, or Firm-Stevens, Davis, Miller & Mosher [5 7] ABSTRACT A process for producing a graft 00- or terpolymeric thermoplastic resin consisting of an ethylene propylene rubber and an aromatic vinyl compound or of an ethylene-propylene rubber, an aromatic vinyl compound and a vinyl cyanide compound, characterized by subjecting these materials to solution polymerization in a mixed solvent comprising an aromatic hydrocarbon solvent capable of dissolving the ethylenepropylene rubber and a polar solvent capable of dissolving poly-( aromatic vinyl compound) in the case of the graft-copolymer or aromatic vinyl compound-vinyl cyanide compound copolymer in the case of the graftterpolymer. The graft-copolymer or graft-terpolymer obtained by the present process is excellent in weather resistance and impact resistance. The impact resistance of the present graft 00- or ter-polymer is not affected by processing conditions.

8 Claims, 4 Drawing Figures PATENTEU SEP 9 7 SHEET 1 [IF 2 PATENTED SEP 91975 SHEET 2 I]? 2 PROCESS FOR PRODUCING HERMOPLASTIC RESINS This invention relates to a process for, producing a thermoplastic resin excellent in impact resistance. More particularly. this invention relates to a solution polymerization process for producing a graftcoor ter-,

polymer consisting of an ethylene-propylene rubber and an aromatic vinyl compound or of both and a vinyl cyanide compound. a 1

It has hitherto been attempted, in'view of the fact that an ethylene-propylene rubber is excellent in weat-' her resistance, to develop a process forproducing a graft-copolymer excellent in both impact resistance and weather resistance by graft-copolymerizing styrene or styrene and acrylonitrile on the ethylene-propylene rubber. ,Most of such processes which have hitherto been known are'abulk polymerization method (U.S.

graft copolymer having an impact resistance comparablc to that of an ABS resin, the impact strengthof such a graft copolymer is greatly affected by processing conditions.

Althoughvarious attempts have heretofore been made to obtain a graft-copolymer having impact resistance substantially not affected byprocessingconditions, that is impact resistance whose dependency on processing conditions issmall, yet no processes have so far been known for producing such a graft-copolymer,

and it has been even considered that-said dependency is aproblem associated primarily withtheuse of an ethylene-propylene rubber..

As aresult-ofextensi e studies to improve the above mentioned dependency of the impact'resistance of a graft-copolymer obtained by using an ethylene propylene rubber as a rubber component, the present inventors have found a novel process for producing a graft-copolymer consisting of an ethylene-propylene rubber and an aromatic vinyl compound or a graftterpolymer consisting ofun ethylene-propylene rubber,

an aromatic vinyl comp'ound, and a vinyl cyanide compound, which has impact resistance hardly affected by processing conditions, that is", an excellent stability against changes in' processing conditions. The present inventors have also found that the wide fluctuation in impzictresistance of the conventionalgraft-copolymers depending upon processing conditions is due to a marked difference in microstructure before and after processing. i v

An object of this invention is to provide a process for producing a graft-copolymer or a graft-terpolyrner in which an aromatic vinyl compound or an aromatic vinyl compoundand a vinyl cyanide compound are grafted onan ethylcnc-propylenc rubber, which has lhi: pact resistancenot affected by processing conditions.

Another object of this invention is to provide a process for producing a graft-copolymcrhaving excellent impact resistance. I A

A further object of this invention is to provide a. process for producing a graft-copolymer, the microstruo,

ture of which will not beehanged in any of the processing, steps (under any processing conditions).

Other objects and advantages of this invention will be apparent to those skilledinthe art fromthe following description.

According to this invention, thereis provided a processfor producing a graft-.copolymeric orterpoly meric; thermoplastic resin consisting of an ethylene-propylene rubber andari aromatic vinyl compound or of an ethyl;

enepropylene rubber, an aromatic vinyl compound and a vinyl cyanide, compound; characterized by subjecting thesematerialsto solution polymerization in a mixed solvent of an,aromatic. hydrocarbon, solvent capableof dissolving the ethylene-propylene rubber and,,a polarsolvent capable of dissolving poly-( aromatic vinyl compound) in the case of the graft-copolymer or aromatic vinyl compound-vinyl cyanide compound copolymer in the-case of the graft-terpolymer. The graft-copolymers orterpolymers obtained by the process of this invention haye such excellent performance characteristics as prominent stability to process ing, substantially no reduction in impact resistance dur+ ing processing, and capability of producing a shaped.

article of smooth surface appearance.- Moreover, the process of this invention hasan advantage inthat since the viscosity of the polymerization .system is markedly low as compared with a conventional process, the re-V moval of the reaction heat by agitation and the after trcatmcntproeeduresare easily carried out.

The term ethylene-propylene rubber .usedherein, means not only a copolymer of ethylene and propylene,

(hereinafter referred to as EBM) but also an ethylenepropylene terpolymer (hereinafter, referred to as, EPDM) composed ofethyle ne, propylene and; as third component, for example, dicyclopentadiene, ethylidenenorborene, 1,4-hexadiene, 1.,5-hexadiene, Z-methyLLS-hexadiene, l,4.-cycloheptadiene, or 1,5- cyclooctadiene alone or in combination.

An ethylene-propylene rubber comprising ethylene and propylene in a molar ratio of 5:1 to 1:3 ,is preferably used. In the case of EPDM, a preferable proportion it of unsaturation is 4 to 50 in terms of iodine value. In this invention,. it is possible to use the ethylene.- propylene rubber jointly with one or more other rubbers; for instance, it is possible to use, a rubber compo nent, a blend of EPDM or EPM with oneor two members or polybutadiene, polyisoprene, styrene-butadiene rubber, and the like. Theselrubbersother than the ethylene-propylene rubber can suitably be selected according to theintended object.,However, when weather resistance is aimed at, the higher the proportion of the ethylene-propylene, rubber in therubber COmPOHCIILQ the better; forexample, a preferred proportion is within the range from 50 to 100. A by weight. 7

The aromatic vinyl; compounds to be used include, for example. styrene, oz-mcthylstyrene, a chlorostyrcne, dimcthylstyrcnc, etc., styrene being preferred. The Vinyl cyanide compounds for use include, for instance, acrylonitrile and methacrylonitrile, i

The weight ratio of the vinyl .compoundsto, ,therubbers may'suitably be selected according to the object; H,

in general, 5 to 20 by weight of the rubber component is used for 95 to 80 7: by weight of the vinyl monomers. On the other hand, inthe case where a graftcopolymer is produced for the purpose of improving the compatibility with other rubbers or resins, it is preferable for increasing the degree of grafting thatthe weight ratioofthe rubber component to the vinyl com ponent is as large as possible. For example. asuitable proportion of the rubber component is within the range from. to 9().'/r.by weightbased on the vinyl monomers.

When the aromatic vinyl compound and the vinyl cyanide compound aregraftcdon the ethylene-propylene rubber, the wcightratioofboth monomers is adjusted within the range fromfilzl to.5:1,; for example. in the case .Of ,Copolymerizing styrene and acrylonitrile. a weight ratio of 10:30 to 75:25 is most suitable.v

Thejaromatic hydrocarbon solvents for'use in this invention must be ,thoselwhich dissolve-the ethylenepropylcne rubbcrssuch as, for example, benzene, toluene,, dimethylbenzenes, xylene, ethylbenzenc, diethyl benzenes, andtricthylbenzenes Thepolarsolvents to be used'in this invention may dissolve the ethylene-propylene rubber, and must dis-" solve at. least a poly-(aromatic vinyl compound) or a copolymer ofthe aromatic vinyl compound and the, vinyl cya nide compound. Examples of. suchsolvents inelude ketonessuch as acetone, methyl ethyl kctone, methyl n-propyl ketone, diethyl ketone, 2-hcxanone,, 3-hexanone, aeetophenone, and propiophenone; esterssuch as methyl formate, ethyl formate, methyl acetate, I

ethyl acetate, n-propyl acetate, n-butyl: acetate, ,n-amyl acetate, methyl propionate, methyl n-butyrate, and the like. cthers such as tctrahydrofuran and dioxane; chlorine-substituted aliphatic hydrocarbons such as dichloroethane and chloroform; nitrogen-containing hydrocarbonssuchas pyridinc aniline, acetonitrile, and dime thylformamide; and sulfur-containing hydrocarbons One or more s lvents selected from each of the-- aboye+mentionedtwogroups of solvents are used as polymerizationmedia in this invention. For example, a

solvent system comprising one or more of the above mentioned hydrocarbon solvents and one or-more of the abovcsmcntioncd. polarsolvents may beused. A mixed solvents of5 to 95% by weight of a hydrocarbon solventand 95 .to 5 7( by weight of a polar solvent is ordinarily used. lt-is also possible to use either oneof the solvents at the initial stage of, polymerization and add the other solventwith proceeding of polymerization.-

The best resultsare obtainedparticularly by using at the initial stage of polymerization a hydrocarbon solventcontaining 0 to 20 7! by weight of a polar solvent.

and adding the polar solvent as the polymerization proceeds until the solvent systcmcontains 40 to "/1 by weight of thepolar solvent at the final stage of polymerization. The rate of polymerization as wellas the state of dispersion of rubber can be freely controlled. by regulating timing and quantity in adding .the polar solvent as the polymerization proceeds.

Common radical polymerization c'atz'ilystsare used as the grafting reaction catalyst. Examples of suitable catalysts are peroxides such as benzoyl peroxide, lauroyl peroxide. di-tertbutyl peroxide, acetyl peroxide, tertbutylperoxypivalate, tcrt-butylperoxybenzoic acid, dicumylperoxide, peroxybenzoic acid, and peroxy-acetio acid; and vdiazo compounds such as azobisisobutyronitrile,

In this invention, the polymerization catalyst may be added in portions. As compared with the additionof a radical catalyst all at one time at the beginning of polymerization, the portionwisc addition has such advantages as acceleration of polymerization, reduction in polymerization time and improvement .in physical properties of the end product. The vinyl monomers are also added preferably in portions, because it is possible to obtain in this-case apolym'er with'higher degree of grafting and having superior physical properties as compared with the case of adding as a whole.

The grafting catalyst is used in anamount'of 0.1 to 10 "/0 by weight on vinyl monom'ers. The polymerization temperature is 30 to 120C, 21 temperature of 50 to C. being particularly suitable. The polymerization time depends to a great extent on polymerization conditions, and is 'desirably controlled so that co'nver sion'may reach 7r or higher inS to'40 hours.

To separate the polymerization product after completion of polymerization, the reaction mixture is poured into a lower alcohol such as methanol or-ethanol with mild agitation to separate thepolymerizate in theform ofa thick paste swollen with the solvent. The separated polymerizate is formed into a sheeting on a roll mill, then dried by being left standing, and finally dried in vacuo at to C for several hours. The

dried polymer is, formed by means ofa pelletizer into pellets of suitable size.

The graft-copolymers obtained according to this invention have an excellent impact rcsistanceand their physicalproperties are hardly affected by processing conditions such as, for example, temperature, pressure and shear stress. a result of examinations on the reason for such an excellent stability, it was found that the graft-copolymers obtained according to this invention has a microstructure essentially differentfrom that ,of conventional I graft-copolymers which were disclosed in, for example, US. Pat. Nos. 3,538,190 or 3,538,l9l, and that fluctuation in impact resistance of graftcopolymers obtained by the conventional processes such as, for example, those disclosed in"U.S. Pat. Nos. 3,538,190or 3,538,191 is associated'with a marked difference in microstructure before and after processing. It may'be said that the present invention have found a process for producing a graft-copolymer which shows little difference in microstructure before and after processing, that is, little dependence upon processing conditionsjand, moreover, has a higher impact resistance as compared with "a conventional grafflcopolymer. Some explanation will be given below regarding microst'ructurc of a graft-copolymer.

In terms of the seaand island concept, as described in, for example, G. E. Molou, Colloid and Morphological Behavior of Block and Graft Copolymer (published by Plenum'Prcss C0,, 1971 microstrueture of thegraft-eopolymer obtained according to this invention is expressed in such a manner that the rubber component forms the island and other components for the sea. Thegraft-copolymer of this invention shows little change in the microstructure even after having passed through processing steps such as milling on a roll mill and extrusion. On the contrary. the graft-copolymers obtained by the solution processes disclosed in US. Pat. Nos. 3,538.190and 3.538. l9l show a reversed mierostructure beforeprocessing; and the microstructurc differs before and after processingdepending upon processing Conditions.

[n the accompanied drawings,

- vl0. FIG. 1 and FIG. 2'are eleetron'mier'ographs of a conrubberstyrene;

acrylonitrile terpolymer before and 111161; processing.

tion, the reaction mixture was poured into methanol to separate a graft-eopolymer. The separated copolymer was made into a sheet by means of rolls and dried in vacuo at l50C.'for 3 hours. i a V 3' I V Measurements of physical properties were conducted in the following manner: A graft-copolymer was mixed on a 7 in. b X 16 infroll mill at 170C. for'lOr'ninutes. and pressed at 200C." for minutes to prepare a sheet. Dumb-bell-shaped test specimens. JIS pattern No. 3. cut out of the resulting sheet were tested for tensile strength at a stretching speed of 5 mm/min. Measurement of impact strength was conducted according to ASTM D256 5 6. The results obtained were as shown in Table I. In Examples 1 2 to l l3. polymerizatio n was carried out in the same manner. as in Example 1 1. using various solvents shown in Trable .l. Tensile strengths and impact strengths of the resulting respectively. y I graft-copolymcrs were as shown iri Table l. Each 50 g The invention is illustrated below in detail with referof an aromatic hydrocarbon solvent were used to dilute ence to examples. but the invention is not limited to the aerylonitrile and the catalysts. examples. 1 The remainder was used. to dissolve EPDM.

Table 1 Example Solvent EPDM. Acrylo- Styrene. Benzoyl Polymeri- Tensile Impact No. Compound (1;) /1 (by nitrile. g peroxide, 1 vation. strength, strength,

- 1 wt.) g g time. hour ,kg/cm notched lzod. 'kg-ehlcrn" I l-l Toluene 710 Acetone 300 12.3 97.5 292.5 3.9 21.0 345 12.5 l-2 Toluene 7l0 Acetonitrile 300 12.1 306 12.7 l-3 Toluene 710 v 1 DiOXflm: 1 300 1 1.21 19.0 392 14.3 l-4 Toluene 7 l0 i 1 1 1 Ethyl acetate 300 12.6 23.0 335 1 16.3 l-5 Toluene 650 I g Chloroform 650 1 1.7 22.0 360 19.1 Toluene 5 00 I l-6 Ethylene 500 11.3 22.0 343 22.7

dichloride 1 l-7 Toluene 500 Acetone 500 13.1 97.5 292.5 3.9 23.0 309 15.6 Toluene 500 1 1 141' Methyl'eth'yl 500 12. f .f 23.5 3.41 12.7

- 1 ketone 1 Toluene 500 1-9 Dioxarie 500 11.5 97.5 292.5 3.9 21.0 368 14,9

Toluene 500 l-l0 v Ethyl acetate .500 12.0 23.0 364 20.0 Toluene 500 V 1-11 Methyl iSO- 500 '1 1.8 23.0 361 13.9

. butyl ketone 1 I Toluene 600 1-12 Ethylacetute 600 15.4 100 300 2.4 29.5 335 48.6

Toluene 600 1 1 1-13 Ethyl acetate 600 l4.6 100 300 3.2 29.0 356 33.0

EXAMPLES l l to 1 l3. Stability of the iinpact resistance of'the'sample ob- In 610 g of toluene placed in a Z-hter separable flask g m l was w T 'T. provided with a Dimroth condenser, a thermometer, a 1 glass tube for bubbling a gas. a Hopkins cooler. and a as I stirrer with two turbine-type blades. were thoroughly v w I 1 dissolved g of EPDM having an iodine value of 18.7, A 'j', j a Mooney viscosity of 40. and containing 34.7% by Table weight of propylencand ethylideneorborene as a'diene A 2 I I component. To the solution in the flask were added F1199! m ng wflditimis Y5 -m is 9 292.5 g of styrene, 97.5 g of acrylonitrile'diluted with cindlmns f .50 f 1 I d 2 9 f h 1 1 .d' (1.] d 1 notched Izod.

g 0 to ucngi 0 p c. Temperature Time. min. Nip. mm. kg-cn1/c n1"" w1th 50g of toluene. Wh1le rotatmg the stirrer at 600 r I y r g rpm. polymerization was allowed'to proceed under an g atmosphere of argon at C. When conversion g m M j reached l5 7!. 300 g of acetone was added dropwise 1 53: 1 and the reaction wasI continued until conversion g reached "/1 or higher. After completion of the reae- V R I Ta ble i-Continucd Effect of mixing conditionswv 'hcn a ro llemill is used. Y Milling conditions Impact resistance.v

Effect of pressing conditions Pi'essing'condit'ions' Impact resistance.

=Tempera- Time. min'. Cooling notched Izod. tur e,(. l kg-cm/cm 180 10 'Rapid 21.7

I80" III 4 Rapid 22.4

200 l() Rapid 35.01;. 200 10 Slow 24.24 200 20 Rapid 23.8

200 20 Slow 24.7

Pressing conditions: I. I

Preheating: 200C, 5 minutes; pressurizingz. I to I00 kg/em 3 minutes; pressing:

1.00. kg/cmi 2.minutes; rapideooling: tap water. minutes; slow cooling: natural cooling.

Comparative Example 1 Following the procedure of Example I, polymerization was conducted in a mixed solvent system comprising n-hexane and toluene, as described in US. Pat. No. 3,538, I90. The relation between processing conditions and impact resistance was as shown in Table 4.

Table 4 Effect of mixing conditions when a roll-mill is used Milling conditions Impact resistance.

Tcmpera- Time. min. Nip. mm. notched Izod, ture.C lt'g-cm/cm I70 IO 0.3 2L3 I 70 3 0. I 17.4 170 5 0 7.7 l7(l ll) 04 l 2.2 I70 20 (l. l 2.3 I70 30 I). l 2. 1 I70 I0 ().()I 2.l

Electron microscopic photographs before and after processing ofa copolymer obtainedin Example I anal! conventional graft-copolymer obtained by polymerizing in toluene solvent in a manner similar to that in Example I were as shown in FIGS. 1 to 4. The ultrathin sections for use in the electron microscopic photography were prepared in the following manner:

In the case of a sample before processing, a film was cast from the polymerization solution and the film was then cut to ultrathin seetions. Aprocessed sample was milled ona roll-mill and then pressed to form a film which was cut to ultrathin sections.

FIG. I and FIG. 2 show respective sections of unprocessed and processed samples ofa cop'olymer pr cpared by a known process, while FIG. 3 andzFlG. 4 show re spcctive sections of unprocessed and'proccssed samples of a copolymer prepared by the present process. Magnification of the electronmicroscopic photograph was 13,000 and hence a length of I .3 cm in the photograph corresponds to I a. I l v l As is'clearly seen from FIGS. 1 to 4. the type of rubher dispersion in the grzttt ct)pt)ly'mer of this invention differs markedly from that in a copolymerpbtained by polymerization in a hydrocarbon solvent. as disclosed in US. Pat. No. 3,538,190. In the former type of rubber component forms island and the styrene-acrylonitrile copolymcr forms sea, while the reverse is the case with 10 the Iat tertype- When these copolymers are treatedby a roll-mill or an. extruder; the former. type shows substantially nochange, whereas in the latter type, the seato-island relation is reversed, that is to say, the rubber component becomes island and the styreneacrylo'nitrile:copolymer becomes sea. The abovementionedfaet'corresponds to the fact that impactresistancc of the graft-copolymcr of this invention is not significantly affected by processing steps. whereas that of a conventional eopolymcr is markedly affected.

EXAMPLE 2 Polymerization was carried out in a mixed solvent 7 comprising 600g of toluene and 600 g of ethyl acetate 60 bladesg'and a dropping funnel, were charged 500 g of toluene an d 50,.() g of an EPD M havingan iodine value of 17.5, a Mooney viscosity of 77 and apropylene con-.

for 23 hours in the same manner as in Example I 13, except that polymerization temperature was 60C. There was obtained a graft-copolymer containing 12 /0 of rubber component and having the following physical properties: I

Tensile strength: Notched Izod impact strength:

EXAMPLE 3 In a manner similar to that in Example I I3 and 'using an.EPDM which had an iodine value of 18.0, a Mooney viscosity of 75, and a propyleneedntent of 40.0 "/1 by weight and contained ethylidenenorbornene as a diene component, polymerization was'conducted in amixed solvent of 600g of toluene and 600 g of ethyl acetate. The catalyst was added in two portions, one half being added at the beginning and the remainder during polymerization. Physical properties of the resulting graft-copolymer (rubber content, 12.3 7:) were as shown below.

' l EXAMPLE 4 In a Z -Iitcr', separable fl aslje providc d with Dimaroth condenser. a thermometer. a glass tube for bubbling a gas. aHopkins coolcna stirrer with two turbine-type tent of 44.6'and containing ethylide nenorbornene as a dienc component. After thorough dissolution had been con-firmed. to the solution were added g of styrene, I

16.7 g of acrylonitrile diluted with 25 of toluene and I g of benzoyl peroxide diluted. with 25 'g of toluene.

\Vhile agitating with a stirrer rotating at 600 rpm, polytrtreatment was c 'ar'r ied out in similar to that, l t) in Example 1 to 'obt'ain a g ra ft copolymerhavingja rubber content of 12.4 Physical properties of this copolymer were as shown' below. I

Tensile strength: 1-

402 ltg/cm S Notched Izod impact strength: 31.3 lfgxm/cnfn EXAMPLE 5 In a manner similar to that in Example 1 l3 and using a rubber component a blend of g of a polybutadiene. NF A" (produced by Asahi Chemical Industry Co.) and g of EPDM used in Example 1. poly- 25 merization was conducted in a mixed solvent of 600 g of toluene and 600 g of ethyl acetate for 32 hours to obtain a graft-copolymer of 1 1.8 rubber content. Physical properties were as shown below.

Tensile strength:

27.4 kg-cm/cm EXAMPLE 6 In a polymerization apparatus similar to that in Example 1, g of the same EPDM as used in Example 1 was dissolved in 550 g of toluene. To the solution, were added 400 g of styrene and 4 g of benzoyl peroxide diluted with g of toluene. Polymerization was conducted under an atmosphere of argon at C., while being stirred with a stirrer rotating at 600 rpm. When conversion reached 50 7c, 600 g of ethylene dichloride was added dropwise and polymerization was carried out for 23 hours to obtain a graftcopolymer of 10.2 rubber content. Physical properties of the copolymer were as shown below 275 kg/cm 1342 kg-cm/cm Tensile strength: Notched Ivod impact strength:

EXAMPLE 7 1:; l0 rubber content. Physical properties of the copolymer were asshown below,, '3 i I a; l

Notched Izod impact strength:

7 EXAMPLE 8 In a polymerization apparatus similar to that used in Exampleyl 2 5 g"'of thesame EPDM as used in Example 1 and 20 g of SBR 1507 (produced by Japan Syn-v thetic Rubber Co's) weredissolved in 550g of toluene. r 1 Tothe solutionwereadded 400 g 'of styrene, '3 g of benzoyl peroxide diluted with SO-g of toluene, and 600 g of methylrethyl' ketone'. Polymerization-was conducted under an atmosph'ereofiargon 'at"70C. for 24 hours,

20 wli'ilebeiiig stirred-witha stirrer rotating at 800 rpm, to

obtain a graft-copolymer of 13 rubber content. Physical properties of th''copolymer were as shown below.

250 kg/crn 16.7 kg-em/em What is claimed is:

1. In a process for producing a graft-co or terpolymeric thermoplastic :resin consisting of an ethylenepropylene rubber and an aromatic vinyl compound or of an ethylene'propylene rubber, an aromatic vinyl compound anda-vinyl cyanide compound by using a radical catalyst, the improvement which comprises subjecting these materials to solution polymerization at a temperature of 30 to 120C for 5 to 40 hours in a mixed solvent consisting of to 5% by weight of at least one aromatic hydrocarbon solvent capable of dissolving the ethylene-propylene rubber and 5 to 95% by weight of at least one polar solvent capable of dissolving poly (aromatic vinyl compound) in the case of the graft-copolymer or aromatic vinyl compound-vinyl cyanide compound copolymer in the case of the graft-terpolymer, the aromatic hydrocarbon solvent being selected from the group consisting of benzene, toluene, di-

methylbenzene, xylene, ethylbenzene, diethylbenzene, and triethylbenzene,

the polar solvent being selected from the group consisting of ketones, esters, ethers, chlorinesubstituted aliphatic hydrocarbons, nitrogen 55 W containing hydrocarbons and sulfur-containing hydrocarbons,

the ethylene-propylene rubber comprising ethylene and propylene in a molar ratio of from 5.1 to 1:3 and being selected from the group consisting of two-component polymer comprising ethylene and propylene and ethylene-propylene-diene terpolymer containing as the third component a diene selected from the group consisting of dicyclopcntadiene, ethylidenenorbornene, 1,4-hexadiene, 1- 5-hexadiene, 2-methyl-l, 5hexadiene, 1,4-

cycloheptadiene, 1,5-cyclooctadiene and mixtures thereof and having an iodine value of 4 to 50,

the aromatic. vinyl component being selected from the group consisting of styrene, oz-methyls'tyrene a-chlorostyrcne and diemthylstyrcne. and the vinyl cyanide compound being selected from the group consisting of acrylonitrile and methacrylonitrile. v l 2. A process according to claim 1, wherein the solution polymerization is effected in the presence of a radical polymerization catalyst in an amount of(). l l "/1 by weight based on the total weight of the vinyl monomers. v I

3. A process according to claim I, wherein the catalyst is added in portions. 3

4. A process according to claim I, wherein the polar solvent is at least one member selected fromthc group consisting of acetone, methyl ethyl ketonc, methyl.npropyl ketonc, dic thyl ketone. 2-hexanone. hexanone, acetophenonc, propiophenone, methyl formate, ethyl formate. methyl acetate; ethyl acetate, n-

propyl acetate, n-butyl acetate, n-amyl acetate. methyl propionate. methyl n-butyrate, tetrahydrofuran, dioxanc. dichloroethane, chloroform; pyridine. aniline, ace-f tonitrile. dimethylformamide and dimethyl sulfoxidc A 5. A process according to' claim 1 wherein the catalyst is selected from the group consisting of bcnzoyl peroxide. lauroyl peroxide, di-t-butyl peroxide, acetyl peroxide, t-butyl p'eroxybe nzoic acid, dicurnyl peroxidc. peroxybenzoic acid; peroxyacetic acid. tert- 7. A process according to claim 1, whereinstyreijief and acrylonitrile are graft-copolymeriz'ed ina weight ratio of :30 to :25 on the rubber.

8. A process according to claim 1, wherein'95 to by weight of the aromatic vinyl or a mixture of the aromatic vinyl and the vinyl cyanide is graftcopolymerized on 5 to 20% by weight of the rubberbased upon the weight of combined monomer and rubher. 

1. IN A PROCESS FOR PRODUCING A GRAFT COPOLYMER WHICH COMTHERMOPLASTIC RESIN CONSISTING OF AN ETHYLENE-PROPYLENE RUBBER AND AN AROMATIC VINYL COMPOUND OR OF AN ETHYLENE-PROPYLENE RUBBER AN AROMATIC VINYL COMPOUND AND A VINYL CYANIDE COMPOUND BY USING A RADICAL CATALYST THE IMPROVEMENT WHICH COMPRISES SUBJECTING THESE MATERIALS TO SOLUTION POLYMERIZATION AT A TEMPERATURE OF 30* TO 120*C FOR 5 TO 40 HOURS IN A MIXED SOLVENT CCONSISTING OF 95 TO 5% BY WEIGHT OF AT LEAST ONE AROMATIC HYDROCARBON SOLVENT CAPABLE OF DISSOLVING THE ETHYLENE PROPYLENE RUBBER AND 5 TO 95% BY WEIGHT OF AT LAST ONE POLAR SOLVENT CAPABLE OF DISSOLVING POLY (AROMATIC VINYL COMPOUND) IN THE CASE OF THE GRAFTCOPOLYMER OR AROMATIC VINYL COMPOUND-VINYL CYANIDE COMPOUND COPOLYMER IN THE ASE OF THE GRAFT-TERPOLYMER THE AROMATIC HYDRCARBON SOLVENT BEING SELECTED FROM THE GROUP CONSISTING OF BENZENE TOLUENE DIMETHYLBENZENE XYLENE ETHYLBENZENE DIETHYLBENEZENE AND TRIETHYLBENZENE THE POLAR SOLVENT BEING SELECTED FROM THE GROUP CONSISTING OF KETONES ESTERS ETHERS CHLORINE-SUBSTITUTED ALIPHATIC HYDROCARBONS NITROGEN CONTAINING HYDROCARBONS AND SULFUR-CONTAINING HYDROCARBONS THE ETHYLENE-PROPYLENE RUBBER COMPRISING ETHYLENE AND PRPYLENE IN A MOLAR RATIO OF FROM 5.1 TO 1,3 AND BEING SELECTED FROM THE GROUP CONSISTING OF TWO-COMPONENT POLYMER COMPRISING ETHYLENE AND PROPYLENE AND ETHYLENE-PROPYLENE-DIENE TERPOLYMER CONTAINING AS THE THIRD COMPONENT A DIENE SELECTED FROM THE GROUP CONSISTING OF DICYCLOPENTADIENE ETHYLIDENENORBORNENE 1,4-HEXIDIENE, 1-5-HEXADIENE, 2-METHYL-1, 5-HEXADIENE, 1,4CYCLOHEPTADIENE, 1,5-CYCLOOCTADIENE AND MIXTURES THEREOF AND HAVING AN IODINE VALUE OF 4 TO 50, THE AROMATIC VINYL COMPONENT BEING SELECTED FROM THE GROUP CONSISTING OF STYRENE, A-METHYLSTYRENE, A-CHLOROSTYRENE AND DIEMTHYLSTYRENE, AND THE VINYL CYANIDE COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE AND METHACRYLONITRILE.
 2. A process according to claim 1, wherein the solution polymerization is effected in the presence of a radical polymerization catalyst in an amount of 0.1 - 10 % by weight based on the total weight of the vinyl monomers.
 3. A process according to claim 1, wherein the catalyst is added in portions.
 4. A process according to claim 1, wherein the polar solvent is at least one member selected from the group consisting of acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, 2-hexanone, 3-hexanone, acetophenone, propiophenone, methyl formate, ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, methyl propionate, methyl n-butyrate, tetrahydrofuran, dioxane, dichloroethane, chloroform, pyridine, aniline, acetonitrile, dimethylformamide and dimethyl sulfoxide.
 5. A process according to claim 1, wherein the catalyst is selected from the group consisting of benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, acetyl peroxide, t-butyl peroxybenzoic acid, dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, tert-butylperoxypivalate and azobisisobutyronitrile.
 6. A process according to claim 1, wherein the weight ratio of the vinyl aromatic compound to the vinyl cyanide compound is 2:1 to 5:1.
 7. A process according to claim 1, wherein styrene and acrylonitrile are graft-copolymerized in a weight ratio of 70:30 to 75:25 on the rubber.
 8. A process according to claim 1, wherein 95 to 80% by weight of the aromatic vinyl or a mixture of the aromatic vinyl and the vinyl cyanide is graft-copolymerized on 5 to 20% by weight of the rubber based upon the weight of combined monomer and rubber. 